JPH0782496A - Perfluoroalkylsulfonylphenylazo-based compound and perfluoroalkylsulfonylaniline-based compound - Google Patents

Abstract

PURPOSE:To produce a new azo-based compound useful as various kinds of pigments, e.g. a disperse dye, a pigment for sublimation type heat-sensitive recording and a pigment for plastics. CONSTITUTION:An azo compound of formula I (K is a coupling component group composed of an aniline-based compound or a tetrahydroquinoline-based compound; n is an integer of 1 to 10), e.g. the compound of formula II. This compound is synthesized by diazotizing a perfluoroalkylsulfonylaniline-based compound or a perfluoroalkylsulfonyl-based compound and coupling an aniline- based compound or a tetrahydroquinoline-based compound therewith.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel azo compound and an aniline compound which is a raw material thereof.
More specifically, the present invention relates to an azo compound useful as a dye, particularly a disperse dye or a dye for sublimation-type heat-sensitive transfer, and a compound extremely useful as an intermediate thereof.

[0002]

2. Description of the Related Art Azo dyes are widely used as disperse dyes and dyes for sublimation-type heat transfer because they are relatively easy to synthesize and inexpensive. As the anilines used as the diazo component when preparing the azo dye, the absorption wavelength is deepened,
Nitroaniline and cyanoaniline have been used to increase the molecular extinction coefficient. However, when these substituents are introduced into the azo dye, the dyeability of the polyester fiber is deteriorated, the solubility in an organic solvent is low, which makes it difficult to process the dye. It may be difficult to do so.

[0003]

DISCLOSURE OF THE INVENTION The object of the present invention is to solve the problems of poor dyeability, low solubility in organic solvents, poor sublimability, etc., and a novel azo dye useful for its production. To provide raw materials.

[0004]

The object of the present invention is to claim 1.
It is an object of the present invention to provide an azo compound represented by the general formula [I] described above and an aniline compound represented by the general formula [III] as a raw material thereof. The present invention will be described in detail below.

Examples of the group K of the coupling component in the above general formula [I] include groups of aniline compounds having various substituents or tetrahydroquinoline compounds represented by the following general formula [IIA] and the like. Particularly, the group represented by the general formula [II] described in claim 2 is preferable.

[0006]

[Chemical 4] (R represents an alkyl group, Q represents a hydrogen atom or various substituents)

When dyeing polyester fiber as a disperse dye in the azo compound of the present invention, the compound represented by the following formula [IV] is represented by the following formula [V] because of its good light fastness. The compound represented by the following formula [VI] is preferable in that the compound represented by the following formula [VI] has a good fastness to sublimation, since the absorption wavelength of the compound is long.

[0008]

[Chemical 5]

In addition to the compounds described in Examples below, examples of preferred compounds in the present invention include compounds of the following formula [VI
The compounds of formula [I] to formula [X] can be mentioned.

[0010]

[Chemical 6]

The polyester fiber dyeing cloth obtained by using the azo compound of the present invention as a disperse dye has a vivid red color tone and good light fastness and sublimation fastness. Further, the azo compound of the present invention has a high solubility in various organic solvents, and thus is useful as an optical filter and a coloring agent for plastics, and since it has a good sublimation property, it is also useful as a dye for sublimation-type thermal transfer.

The method for synthesizing the perfluoroalkylsulfonylaniline represented by the general formula [III] of the present invention is as follows. A perfluoroalkylthionitrobenzene (p-nitrothiophenol represented by the formula [XI] is used as a raw material as shown in the following reaction formula. It can be synthesized via the general formula [XII]) and perfluoroalkylsulfonylnitrobenzene (general formula [XIII]). This reaction is represented by the following reaction formula.

[0013]

[Chemical 7]

The reaction for obtaining perfluoroalkylthionitrobenzene [XII] from p-nitrothiophenol [XI] is preferably carried out in a solvent. The solvent is not particularly limited, but a polar solvent is preferably used, for example, dimethyl. Formamide, tetrahydrofuran, alcohol and the like are used. In these solvents, a halogenated alkyl compound represented by _{p- nitrothiophenol} and C _p F _{2p + 1} Y (wherein p is an integer of 4 to 8 and Y represents a bromine atom or an iodine atom). Is reacted in the presence of a suitable alkali such as potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, triethylamine and the like.
The reaction can be carried out at −10 ° C. to 40 ° C., preferably 20 ° C. or lower, particularly preferably 5 ° C. to 10 ° C. Further, a catalyst such as crown ether or phase transfer catalyst may be added to the reaction system.

Before adding the halogenated perfluoroalkyl compound represented by C _p F _{2p + 1} Y, p-nitrothiophenol is previously reacted with sodium hydride, sodium metal, sodium alcoholate, sodium amide or the like to give a thioalcoholate. Is preferred, and then the halogenated perfluoroalkyl compound is reacted, because the synthetic yield is high. Further, a method using sodium hydride is particularly preferable from the viewpoint of reactivity, but an alkali compound such as potassium hydroxide or sodium hydroxide can be used instead of sodium hydride.

The reaction of oxidizing perfluoroalkylthionitrobenzene [XII] to obtain perfluoroalkylsulfonylnitrobenzene [XIII] is carried out in a solvent using various oxidizing agents such as hydrogen peroxide, potassium permanganate, sodium dichromate and chromic anhydride. Can be done by adding. Further, air oxidation may be performed instead of these oxidizing agents. As the solvent, various ones that are stable against an oxidizing agent, such as water, various organic solvents, various acids such as acetic acid and sulfuric acid, can be used. The reaction using hydrogen peroxide in acetic acid and the reaction using chromium oxide in acetic acid are particularly preferable because the yield is good.

The reaction for reducing perfluoroalkylsulfonylnitrobenzene [XIII] to obtain perfluoroalkylsulfonylaniline is carried out, for example, by using various reducing agents exemplified in "Chemistry of Synthetic Dyes" by Kenzo Konishi and Nobuhiko Kuroki, page 64, Maki Shoten. It can be done using. Typical examples are iron, zinc or tin and an acid, zinc or iron and a strong alkali, zinc and a weak alkali, and the like. The reaction using iron and concentrated hydrochloric acid is particularly preferable because the yield is high and the reaction rate is fast.

In the azo compound of the present invention, in addition to the above-mentioned perfluoroalkylsulfonylaniline compounds having p of 4 to 8, perfluoroalkylsulfonyl compounds having p = 1 to 3 and p = 9 or 10 are diazotized, and then aniline compounds are produced. It can be obtained by coupling with a compound or a tetrahydroquinoline compound. The aniline compound as the coupling component is represented by the following general formula [XIV] (wherein R ¹
To R ⁴ are the same as in the general formula [II]. ) And the like, or a compound having a substituent on the benzene ring or amino group of aniline, and the tetrahydroquinoline compound is a compound having various substituents on tetrahydroquinoline or tetrahydroquinoline.

[0019]

[Chemical 8]

As the method of diazotization, various methods such as a method of acting sodium nitrite in hydrochloric acid and a method of acting nitrosyl sulfuric acid in a sulfuric acid solution can be used. When the solubility of the starting diazo component in water is low, it is desirable to add an organic solvent such as dimethylformamide or dimethylsulfoxide because the diazotization reaction proceeds efficiently.

[0021]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1 Sodium hydride (22.0 mmol, 0.88 g) was suspended in dimethylformamide (DMF, 30 ml), and 4-nitrothiophenol (20.0 mmo) was added thereto.
1, 3.10 g) and DMF (30 ml) were slowly added dropwise with stirring at room temperature under nitrogen to give a sodium salt. After standing for 30 minutes, perfluorobutyl iodide (22.0 mmol, 7.61 g) and D were added to the solution.
A mixed solution of MF (30 ml) was added dropwise, and 1 at room temperature under nitrogen.
Stir vigorously for 5 hours. After the reaction, the solution was saturated with saline (1
00 ml). The product is ether (100 m
It was extracted twice with l) and dried over anhydrous sodium sulfate. This was concentrated and recrystallized from hexane to give the compound represented by the general formula [XII].
To give 4-perfluorobutylthionitrobenzene pale yellow crystals of p = 4.

The physical properties of this 4-perfluorobutylthionitrobenzene were as follows. Yield 83% (6.19 g); Melting point 40.0 to 42.5 ° C; Mass spectrum EI-MS (70 ev) m / z (relative intensity) 373 (M ⁺ , 100), 204 (56), 12
4 (27), 108 (82), 69 (92); NMR spectrum ¹ H-NMR (CDCl ₃ ) δ 7.86.
(D, J = 8.5 Hz, 2H), 8.29 (d, J =
8.5 Hz, 2H). Elemental analysis: C, 33.14; H, 1.23; N, 3.8
1% (measured value) C ₁₀ H ₄ F ₉ NO ₂ S: C, 32.18; H, 1.0
8; N, 3.75% (calculated value)

Acetic acid (30 ml) was added to the obtained 4-perfluorobutylthionitrobenzene (10.0 mmol, 3.73 g), and the mixture was heated to reflux. 30% there
Hydrogen peroxide (300.0 mmol, 34.0 g) was slowly added dropwise, and the mixture was refluxed for 5 hours. After the reaction, the mixture was neutralized with a saturated aqueous sodium hydrogen carbonate solution (250 ml). The product was extracted twice with ether (125 ml) and dried over anhydrous sodium sulfate. After concentrating this, hexane-methylene chloride mixed solvent (hexane: methylene chloride = 1: 10)
Recrystallization was carried out to obtain 4-perfluorobutylsulfonylnitronitrobenzene pale yellow needle crystals represented by p = 4 in the general formula [XIII].

This 4-perfluorobutylsulfonyldione
The physical properties of trobenzene were as follows. Yield 81% (3.28 g); melting point 125.0-126.5 ° C; mass spectrum EI-MS (70 ev) m / z (relative
Strength) 186 (M⁺-C _FourF₉, 100), 170 (2
1), 122 (93), 76 (66), 50 (77);
CI-MS (i-C_FourH_Ten) M / z (relative intensity) 406
(MH⁺, 100); NMR spectrum¹H-NMR
(CDCl₃) Δ8.28 (d, J = 8.5 Hz, 2
H), 8.52 (d, J = 8.5 Hz, 2H); IR sweep
Vector (KBr) 1545 (ν_as NO₂), 13
78 (ν_sNO₂), 1352 (ν_as SO₂), 11
37 (ν_sSO₂). Elemental analysis: C, 29.96; H, 1.00; N, 3.4
3% (measured value) C_TenH_FourF₉NO_FourS: C, 29.64; H, 0.9
9; N, 3.46% (calculated value)

4-dissolved in methanol (30 ml)
Perfluorobutylsulfonyl nitrobenzene (5.0
concentrated hydrochloric acid (30 mmol, 2.3 g).
5 ml) was added, and the mixture was refluxed with stirring. Iron scraps (22.5 mmol, 1.24 g) were added to the solution in small portions, and the mixture was stirred for 1 hour. After cooling, suction filtration was carried out, the precipitate was subjected to Soxhlet extraction with methanol to obtain a crude product, which was recrystallized from hexane, and p = 4 in the above-mentioned general formula [III].
To obtain 4-perfluorobutylsulfonylaniline.

The physical properties of this 4-perfluorobutylsulfonylaniline were as follows. Yield 70% (1.31 g); Melting point 85.0-86.5 ° C; Mass spectrum EI-MS (70 ev) m / z (relative intensity) 375 (M ⁺ , 22), 156 (100), 14
0 (17), 108 (50), 92 (77), 69 (2
0); NMR spectrum ¹ H-NMR (CDCl ₃ ).
δ4.52 (brs, 2H, NH ₂ ), 6.75 (d,
J = 8.8 Hz, 2H), 7.76 (d, J = 8.8H
z, 2H); IR spectrum (KBr) 3490 (ν
_aS NH ₂ ), 3385 (ν _s NH ₂ ), 1354 (ν
_aS SO ₂ ), 1158 (ν _s SO ₂ ). Elemental analysis: C, 32.12; H, 1.57; N, 3.8
7% (measured value) C ₁₀ H ₆ F ₉ NO ₂ S: C, 32.01; H, 1.6
1; N, 3.73% (calculated value)

Example 2 Sodium hydride (22.0 mmol, 0.88 g) was suspended in DMF (30 ml), and 4-nitrothiophenol (20.0 mmol, 3.10 g) and DMF were suspended therein.
A mixed solution of (30 ml) was slowly added dropwise with stirring at room temperature under nitrogen to obtain a sodium salt. After standing for 30 minutes, the solution was added with perfluorooctyl iodide (22.
A mixed solution of 0 mmol, 12.0 g) and DMF (30 ml) was added dropwise, and the mixture was vigorously stirred under nitrogen at room temperature for 15 hours.
After the reaction, the solution was poured into saturated saline (100 ml).
The product was extracted twice with ether (100 ml) and dried over anhydrous sodium sulfate. This was concentrated and recrystallized from hexane to obtain a pale yellow crystal represented by p = 8 in the general formula [XII].

The physical properties of this mixture were as follows: Yield 93% (10.6 g); Melting point 79.0-81.0 ° C; Mass spectrum EI-MS (70 ev) m / z (relative intensity) 573 (M ⁺ , 33), 204 (100), 15
8 (23), 108 (47), 69 (75); NMR spectrum ¹ H-NMR (CDCl ₃ ) δ 7.86.
(D, J = 8.9 Hz, 2H), 8.29 (d, J =
8.9 Hz, 2H). Elemental analysis: C, 31.83; H, 1.03; N, 2.7
3% (measured value) C ₁₄ H ₄ F ₁₇ NO ₂ S: C, 29.33; H, 0.7
0; N, 2.44% (calculated value)

Acetic acid (30 ml) was added to the obtained 4-perfluorooctylthionitrobenzene (10.0 mmol, 5.73 g), and chromium (VI) oxide (100.0 mmol, 10.0 g) dissolved in acetic acid was further added. Two
Refluxed for 4 hours. After the reaction, after cooling to room temperature, water (1
00 ml). A precipitate was formed, which was filtered by suction, and the obtained product was recrystallized from hexane to obtain white crystals of the compound represented by p = 8 in the above general formula [XIII].

The physical properties of this compound are as follows.
It was Yield 89% (5.38 g); Melting point 155.0 to 156.0 ° C; Mass spectrum EI-MS (70 ev) m / z (relative
Strength) 186 (M⁺-C _FourF₉, 100), 170 (1
7), 122 (94), 92 (23), 76 (42),
69 (38); CI-MS (i-C_FourH_Ten) M / z (phase
Strength) 606 (MH⁺, 100); NMR spectrum
 ¹H-NMR (CDCl₃) Δ8.28 (d, J =
8.2Hz, 2H, H^b), 8.52 (d, J = 8.2)
Hz, 2H, H^a); IR spectrum (KBr) 15
42 (ν_asNO₂), 1372 (ν_sNO₂), 135
0 (ν_asSO₂), 1149 (ν_sSO₂). Elemental analysis: C, 28.93; H, 0.70; N, 2.2
9% (measured value) C₁₄H_FourF₁₇NO_FourS: C, 27.78; H, 0.6
7; N, 2.31% (calculated value)

4-Perfluorooctylsulfonylnitrobenzene (5.0 mmol, 2.88 g) was dissolved in methanol (30 ml), and concentrated hydrochloric acid (30 mmo) was added thereto.
1, 2.5 ml) was added and the mixture was refluxed with stirring. Iron scraps (22.5 mmol, 1.24 g) were added to the solution little by little and stirred for 1 hour. After cooling, suction filtration was carried out, the precipitate was subjected to Soxhlet extraction with methanol to obtain a crude product, which was recrystallized from hexane to obtain 4-perfluorooctylsulfonylaniline represented by p = 8 in the general formula [XIII].

The physical properties of this 4-perfluorooctylsulfonylaniline were as follows. Yield 67% (1.93 g); Melting point 138.0 to 139.0 ° C; Mass spectrum EI-MS (70 ev) m / z (relative intensity) 575 (M ⁺ , 2), 156 (100), 108.
(46), 92 (70), 69 (47); CI-MS
(I-C ₄ H ₁₀ ) m / z (relative intensity) 576 (MH ⁺ ,
20), 126 (100); NMR spectrum ¹ H-
NMR (CDCl ₃ ) δ4.51 (brs, 2H, NH
₂ ), 6.75 (d, J = 8.5 Hz, 2H, H ^b ),
7.76 (d, J = 8.5Hz, 2H, H a); IR spectrum _{(KBr) 3478 (ν as NH} 2), 338
3 (ν _s NH ₂ ), 1335 (ν _as SO ₂ ), 1152
(Ν _s SO ₂ ). Elemental analysis: C, 28.57; H, 0.95; N, 2.4
8% (measured value) C ₁₄ H ₆ F ₁₇ NO ₂ S: C, 29.23; H, 1.0
5; N, 2.43% (calculated value)

Example 3 5-Acetylamino-2-methoxy-4- (4-perfluorobutylsulfonyl-phenylazo) -N , N-
Synthesis of diethylaniline 4 obtained in Example 1 dissolved in DMF (5 ml)
-Perfluorobutylsulfonylaniline (1.33m
concentrated hydrochloric acid (0.4 ml) and water (10 ml)
ml) was added and stirred for 3 hours, and sodium nitrite (1.5 mmol, 0.10 g) and water (5 m) were added to the solution.
The solution of l) was added rapidly at 0 ° C. with stirring. Stirring was continued for 5 hours to promote the diazotization reaction. This diazotized solution was added to 5-acetylamino-2-methoxy- N , N -diethylaniline (1.5 mmol, 0.36 g) dissolved in DMF (5 ml), and made weakly acidic with a saturated sodium acetate aqueous solution (10 ml). Allowed to stir for 15 hours. After the reaction, the mixture was made alkaline with an aqueous sodium hydroxide solution, suction-filtered, and a crude product was obtained by column chromatography (silica gel, hexane: acetone = 2: 1). The compound was obtained.

[0035]

[Chemical 9]

The physical properties of this azo compound (1) are as follows. Yield 44% (0.36 g); melting point 126.0-130.5 ° C; mass spectrum EI-MS (70 ev) m / z (relative intensity) 622 (M ⁺ , 41), 607 (48), 339.
(39), 324 (100), 76 (26), 69 (2
8); NMR spectrum ¹ H-NMR (CDCl ₃ ).
δ 1.26 (t, J = 6.7Hz, 6H, 2xC
H ₃ ), 2.28 (s, 3H, COCH ₃ ), 3.52
(Q, J = 6.7Hz, 4H , 2xCH 2), 3.89
(S, 3H, OCH ₃ ), 7.32 (s, 1H,
H ^d ), 7.92 (d, J = 9.2 Hz, 1H,
H ^b ), 8.10 (d, J = 9.2 Hz, 2H,
H ^b ), 8.21 (s, 1H, H ^c ), 10.19
(S, 1H, NH); visible absorption spectrum (in ethanol) λ _max = 535 nm; ε = 27700.

Example 4 5-Acetylamino-2-methoxy-4- (4-perfluorooctylsulfonyl-phenylazo) -N , N-
Synthesis of diethylaniline 4 obtained in Example 2 above dissolved in DMF (5 ml)
-Perfluorooctylsulfonylaniline (0.87
Concentrated hydrochloric acid (0.22 ml) and water (10 ml) were added to (mmol, 0.5 g) and the mixture was stirred for 3 hours, and a solution of sodium nitrite (1.0 mmol, 0.07 g) and water (5 ml) was added to the solution. It was added rapidly with stirring at 0 ° C. The mixture was stirred as it was for 5 hours to promote the diazotization reaction. This diazotized solution was added to 5-acetylamino-2-methoxy- N , N -diethylaniline (1.0 mmol, 0.24 g) dissolved in DMF (5 ml), and made weakly acidic with a saturated aqueous sodium acetate solution (10 ml). Allowed to stir for 15 hours. After the reaction, the mixture was made alkaline with an aqueous sodium hydroxide solution, suction filtered, and a crude product was obtained by column chromatography (silica gel, hexane: acetone = 2: 1). A methylene chloride-hexane mixed solvent (methylene chloride: hexane = 1: 1) was obtained. Recrystallized in 10), the following formula (2)
A compound represented by

[0038]

[Chemical 10]

The physical properties of this azo compound (2) are as follows. Yield 43% (0.31 g); melting point 114.5-116.5 ° C; mass spectrum EI-MS (70 ev) m / z (relative intensity) 822 (M ⁺ , 20), 807 (12), 339.
(48), 324 (100), 235 (20), 76
(20), 69 (22); NMR spectrum ¹ H-N
MR (CDCl ₃ ) δ 1.26 (t, J = 6.9 Hz,
_{6H, 2xCH 3), 2.28 (} s, 3H, COC
_{H 3), 3.52 (q,} J = 6.9Hz, 4H, 2xC
H ₂ ), 3.89 (s, 3H, OCH ₃ ), 7.33
(S, 1H,), 7.92 (d, J = 8.7 Hz, 2
H), 8.10 (d, J = 8.7 Hz, 2H), 8.2
1 (s, 1H), 10.18 (s, 1H, NH); visible absorption spectrum (in ethanol) λ _max = 533 nm;
ε = 21400.

Example 5 4 obtained in Example 1 above dissolved in DMF (5 ml)
-Perfluorobutylsulfonylaniline (1.5 mm
ol, 0.207 mg), concentrated hydrochloric acid (0.38 ml) and water (10 ml) were added and stirred for 3 hours, and sodium nitrite (1.5 mmol, 0.1 g) and water (5 ml) were added to the solution.
solution) was added at 0 ° C. with stirring. The mixture was stirred at 0 ° C for 4 hours. This diazotized solution was dissolved in DMF to form N-
Cyanoethyl-N-ethylaniline (1.5 mmol,
0.26 g) with saturated aqueous sodium acetate solution
Was maintained at 4-6 and added with cooling to 0 ° C. The reaction mixture was stirred for further 15 hours, and the obtained crystals were filtered to obtain a crudely purified product by column chromatography (silica gel, dichloromethane), which was then recrystallized from hexane to give a compound represented by the following formula (3). Got

[0041]

[Chemical 11]

The yield and physical properties of this product were as follows. Yield 55% mp 139-140 ° C.; NMR spectrum _{(CDCl 3) 1.30 (t,} J =
7.2 Hz, 3 H), 2.71 (t, J = 6.7 Hz,
2H), 3.61 (q, J = 7.2Hz, 2H), 3.
81 (t, J = 6.7 Hz, 2H), 6.77 (d, J
= 9.2 Hz, 2H), 7.95 (d, J = 9.2H)
z, 2H), 8.04 (d, J = 8.8Hz, 2H),
8.13 (d, J = 8.8 Hz, 2H); mass spectrum EI-MS (70 ev) m / z (relative intensity) 560
(M ⁺ , 36), 520 (94), 237 (100),
173 (73); visible absorption spectrum (in ethanol)
λ _max = 456 nm; ε = 21400.

Example 6 To the azo compound obtained in Example 3, a 10-fold amount of formalin polycondensate of sodium salt of naphthalenesulfonic acid and 50 were added.
Double volume of water is added, and to this mixture, glass beads having a diameter of 0.8 mm to 1 mm with a volume of 80% of the total volume are added.
The dye was dispersed by stirring at 0 ° C or lower for 24 hours. A buffer solution containing an aqueous solution of acetic acid and sodium acetate was added to the obtained dispersion liquid to adjust the pH to 5, an appropriate amount of water was added, and a polyester cloth (Tetron amundsen cloth) was dyed at 130 ° C. for 1 hour. The obtained dyed cloth was washed with a 2% sodium hydrosulfite aqueous solution at 90 ° C. for 5 minutes and then washed with water and dried.

The obtained dyed cloth is a clear, slightly bluish red color and has light fastness (JIS L08) at a density of JIS 1/1.
42 Carbon Arc) was 4-5 grade, and sublimation fastness (iron tester 180 ° C, 30 sec judged by JIS contamination gray scale) was 4-5 grade.

Examples 7 to 12 The azo compounds of the present invention shown in Table 1 below, which were synthesized according to the methods of Examples 1 to 5, were dyed according to Example 6 to give fastness to light and sublimation fastness. evaluated. The structural formula, maximum absorption wavelength, light fastness, and sublimation fastness are shown in Table 1 together with the results of Example 6.

[0046]

[Table 1]

[0047]

The azo compound of the present invention is very useful as a disperse dye and various dyes such as dyes for sublimation type heat-sensitive recording and coloring agents for plastics. The aniline compound of the present invention is a very useful compound as a raw material for the azo compound.

Claims (3)

[Claims] 1. An azo compound represented by the following general formula [I]. [Chemical 1] (In the formula, K represents a group of a coupling component composed of an aniline compound or a tetrahydroquinoline compound, and n
Represents an integer from 1 to 10. ) 2. In claim 1, K is the following general formula [II]
An azo compound which is a group represented by: [Chemical 2] [In the formula, R ¹ is a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, or NHC.
OX (in the formula, X represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group which may have a substituent), and R ² represents a hydrogen atom, a methyl group, or ethyl. Represents a group, a methoxy group, an ethoxy group, a chlorine atom, or a bromine atom, and R ³ and R ⁴ each represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or C _m H _2m Z. M represents an integer of 1 to 4, Z represents a cyano group, an alkoxy group having 1 to 4 carbon atoms, COOR ⁵ or OCOR ⁶ . R
⁵ and R ⁶ both represent an alkyl group having 1 to 5 carbon atoms. ] 3. An aniline compound represented by the general formula [III]. [Chemical 3] (In the formula, p represents an integer of 4 to 8.)